The sterically encumbering m-terphenyl isocyanides, CNArMes2 (Mes = 2,4,6-Me3C6H2) and CNArDipp2 (Dipp = 2,6-(i-Pr)2C6H3), have been demonstrated to stabilize highly reactive organometallic species.  Presented here is the synthesis and characterization of a series of Cobalt dimers with a general formulation [Co2(?5-C5H5)2(�-L)2 ]n  (where n = 0, -2 and L = CNArMes2, CNArDipp2). These complexes are isocyanide analogues of classic CpCo-carbonyl dimers. Upon addition of one equivalent of CNArMes2 to (Co(?5-C5H5)CO)2, clean conversion to Co(?5-C5H5)(CO)(CNArMes2) is observed, which can be oxidized by I2 to yield Co(?5-C5H5)(CNArMes2)I2. Treatment of Co(?5-C5H5)(CNArMes2)I2 with KC8 in a thawing diethyl ether solution affords the dianion K2[Co2(?5-C5H5)2(�-CNArMes2)2], which posses marked similarities and differences to its carbonyl counterpart. Similar synthetic steps utilizing CNArDipp2 result in the formation of Co2(?5-C5H5)2(�-CNArDipp2)2. This more hindered dimer undergoes reaction chemistry distinct from the CNArMes2 derivative.

Use of sterically encumbering m-terphenyl isocyanides in the synthesis and characterization of [Co2(η5-C5H5)2(μ-L)2 ]n complexes (n = 0,-2)

245th National Meeting (2013)

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